WO2016177810A1 - Spectromètre de masse en ligne pour la détection en temps réel de composants volatiles provenant de la phase gazeuse et liquide aux fins d'analyse de processus - Google Patents

Spectromètre de masse en ligne pour la détection en temps réel de composants volatiles provenant de la phase gazeuse et liquide aux fins d'analyse de processus Download PDF

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Publication number
WO2016177810A1
WO2016177810A1 PCT/EP2016/060055 EP2016060055W WO2016177810A1 WO 2016177810 A1 WO2016177810 A1 WO 2016177810A1 EP 2016060055 W EP2016060055 W EP 2016060055W WO 2016177810 A1 WO2016177810 A1 WO 2016177810A1
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WO
WIPO (PCT)
Prior art keywords
gaseous
flow element
flow
substances
liquid
Prior art date
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PCT/EP2016/060055
Other languages
German (de)
English (en)
Inventor
Martin Joos
Matthias Stier
Stephan SCHERLE
Original Assignee
Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. filed Critical Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
Priority to US15/568,627 priority Critical patent/US10361072B2/en
Priority to EP16721783.5A priority patent/EP3292563B1/fr
Publication of WO2016177810A1 publication Critical patent/WO2016177810A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0422—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for gaseous samples
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18—Water
    • G01N33/1826—Water organic contamination in water
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0431—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for liquid samples
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0495—Vacuum locks; Valves

Definitions

  • On-line mass spectrometer for real-time acquisition of volatile components from the gas and liquid phase for process analysis
  • the present invention relates to a method for the mass spectrometric analysis of substances present in liquid and / or gaseous samples and to an apparatus for carrying out this method.
  • Process mass spectrometers for analyzing a gas phase are known in the art, for example from Thermo Scientific and Extrel CMS, LLC.
  • DE 41 33 300 AI discloses an "on-line" mass spectrometer
  • Permeate side of the membrane inlet is a pre-vacuum, whereby the liquid is continuously evaporated at the Membranoberfikiee.
  • a rotary valve When a rotary valve is opened, part of the gas stream located in the pre-vacuum, also referred to as a fine vacuum, passes into a high vacuum and is measured there as an ion current in the mass spectrometer.
  • the present method and the present device should be characterized in that the device is installed once in a reaction system and then in real time with a utilization of preferably at least 90%, preferably at least 95%, present in the reaction system and the device can be supplied gaseous and / or liquid samples analyzed completely automated and determines the volatile substances therein and in case of errors or problems independently, preferably software or computer-aided, recognizes these and optionally takes appropriate security measures against it.
  • the invention is therefore based on the object, a method and / or apparatus for the determination of volatile substances or in gaseous form
  • the present invention relates to a method for the mass spectrometric analysis of substances present in liquid and gaseous samples, comprising the steps: a) optional, preferably valve-controlled, introduction of at least one or more
  • Flow element is different from the second flow element, so that the at least one or more substances are at least partially, preferably completely, in gaseous form, and b) mass spectrometric analysis of the at least one or more gaseous substances present in step a).
  • the method according to the invention can be carried out automatically. According to the invention, it is therefore provided, in particular, for at least one substance from a liquid sample to be introduced into a first flow-through element and at least one substance for a gaseous sample into a second flow-through element of the device used according to the invention, that is to say into two different, ie not the same flow-through element.
  • the first flow-through element is from the second
  • the first für fiusselement different insofar as that the first für fiusselement is provided for introducing at least one substance from a liquid sample and the second fürfiusselement for introducing at least one substance from a gaseous sample.
  • the invention preferably provides an aforementioned method according to which, in step a) optionally, in particular valve-controlled, at least one or more substances of a liquid sample in a first fürfiusselement a device for mass spectrometric analysis of existing in liquid and gaseous samples substances and / or at least one or several substances of a gaseous sample in a second fürfiusselement this device, which is different from the first fürfiusselement is introduced, or and wherein this is done so that after introduction of the at least one or more substances in the first and / or second flow element, the at least one or more substances in the first and / or second flow element each present at least partially, preferably completely, gaseous or present.
  • the invention preferably provides a method for mass spectrometric analysis using a device for mass spectrometric analysis of substances present in liquid and gaseous samples, wherein, preferably optionally, in particular valve-controlled, in step a) the at least one or more substances from a liquid, preferably aqueous Sample evaporates, that is, is converted into the gaseous state and then in a first flow member of the device partially, preferably completely, in gaseous state, that is volatilized, is introduced or / and wherein at least one or more substances from the gaseous sample is introduced into a second flow element of the device different from the first flow element, so that after introduction of the at least one or more substances into the first and / or second flow element, the at least one or more Substances at least partially, preferably completely, gaseous in the respective
  • a method for mass spectrometry analysis of substances present in volatile and gaseous samples wherein in step a) at least one or more substances of a liquid sample in a first flow element of the inserted device as well as at least one or more substances of a gaseous Sample are introduced into a second flow element of the device, are introduced in particular offset in time, so that after introduction, preferably after the time-shifted introduction, the at least one or more
  • the at least one or more substances at least partially, preferably completely, gaseous in the respective
  • Flow element present, preferably offset in time.
  • the invention provides, in a method step b), to analyze the at least one substance originating from the liquid sample and the at least one substance originating from the gaseous sample separately by mass spectrometry.
  • a reaction system which contains at least one substance to be analyzed in a liquid and gaseous phase
  • the content of the substances which can be converted into volatile form can advantageously be brought about by introducing at least one substance from a liquid sample and at least one substance from a gaseous sample of the reaction system , eg the total content to the analyte, in the measured
  • Reaction system can be determined from the liquid and gaseous phase.
  • the inventive method is preferably by means of an inventive
  • this device a device for mass spectrometric analysis of existing in liquid and gaseous samples
  • Substances is, comprising at least aa) a mass spectrometer, bb) at least one inlet for a liquid sample and cc) at least one inlet for a gaseous sample.
  • the at least one inlet for the introduction of at least one substance of a liquid sample is preferably an element upstream of the first flow element on the sample side.
  • the at least one inlet for the introduction of at least one substance from a gaseous sample is preferably an element which precedes the second flow element on the sample side.
  • the at least one substance to be analyzed in the liquid sample is present in or at an inlet present in the liquid sample
  • the at least one inlet for the liquid sample can be designed as an in situ sensor having a membrane.
  • the membrane device can also be designed as a membrane device, past which the liquid sample is passed.
  • the present invention provides a method for the mass spectrometric analysis of substances present in a reaction system comprising a liquid and a gaseous phase, comprising the steps:
  • step b) mass spectrometric analysis of the at least one in step a) gaseous
  • step a) when the method according to the invention is carried out in step a), at least one substance of a liquid sample is introduced into a first flow element and, preferably with a time offset, at least one substance of a gaseous sample is introduced into a second flow element, so that is preferred offset in time, in both flow elements, the at least one substance is present in gaseous form.
  • a method according to the invention makes it possible, in a gaseous and a liquid phase reaction system, in particular a closed reaction system, e.g. the total amount of at least one volatile substance in both the liquid and the gaseous phase by means of a single device, namely the invention
  • the method according to the invention makes it possible to provide partial or complete metabolic balances in a wide variety of reaction systems, in particular for a wide variety of reactions, in particular biotechnological reactions.
  • the present invention provides a method in which substances or substance components present in non-volatile form are additionally determined by means of a detector which is optionally present in the device according to the invention for the determination of nonvolatile substances in a liquid phase.
  • an abovementioned process is provided with the steps a) and b), in which process steps a), al), a2) described below, and b), in particular i), ii), iii) and iv ), be performed.
  • the present invention preferably relates to a process wherein, in a step a) preceding step b), the at least one or more gaseous substances are introduced into a third flow element of the device, wherein in the third
  • a pressure of 0.01 to 0.5 mbar, preferably 0.15 to 0.2 mbar is present.
  • the at least one or more gaseous substances from the gaseous sample are preferably introduced into a first third flow element and the at least one or more gaseous substances from the liquid sample are introduced into a second third flow element, wherein in the first and / or second third flow element Pressure of 0.01 to 0.5 mbar, preferably 0.15 to 0.2 mbar is present.
  • the at least one or more gaseous substances from the gaseous sample and the liquid sample are introduced into the same third flow element, in particular offset in time and separated from one another.
  • the present invention preferably relates to a method, wherein in a step a2) lying before step b), the at least one or more gaseous substances are introduced into a fourth flow element of the device, wherein in the fourth fürfiusselement a pressure of 10 "5 mbar or less, preferably 10 "6 mbar or less, preferably 10 -7 mbar or less, preferably 10" 5 mbar to 10 "10 mbar, is present.
  • the at least one or more gaseous substances are initially introduced into the third and then into the fourth flow element.
  • the at least one or more gaseous substances of the gaseous sample are preferably first introduced into a first third flow element and then into a first fourth flow element.
  • the at least one or more gaseous substances of the liquid sample are first introduced into a second third flow element and then into a second fourth flow element.
  • the at least one or more substances present in gaseous form in the first third and the second third flow element are introduced into the same fourth flow element.
  • the invention preferably relates to a method, wherein the mass spectrometric analysis according to step b) comprises the following steps: i) ionizing the at least one or more gaseous substances, ii) accelerating the at least one or more substances ionized in step i), iii) selecting the at least one or more accelerated substances in step ii), and
  • step iii) detecting the at least one or more selected in step iii) substances.
  • the mass spectrometric analysis according to step b) preferably comprises ionizing the at least one or more gaseous substances and subsequently detecting the at least one or more ionized substances.
  • ii) at least partially, preferably partially or completely, accelerating the at least one or more substances ionized in step i), iii) at least partially, preferably partially or completely, selecting the at least one or more accelerated in step ii) substances, and iv) at least partially, preferably partially or completely, detecting the at least one or more substances selected in step iii).
  • the first, the second, the third, preferably the first and / or second third, and / or the fourth, preferably the first and / or second fourth, flow element is a conduit, preferably a tube or a tube, preferably a metal tube or Metal corrugated hose, preferably a stainless steel tube or stainless steel corrugated hose.
  • first, the second, the third and the fourth flow element in particular the first and the second flow element, can be designed identical.
  • the method according to the invention and the device according to the invention are particularly advantageously usable for the quantitative and qualitative determination of volatile substances in a reaction system, which reaction system is made up of a liquid and a gaseous phase, in particular a liquid and a gas or a gas mixture.
  • the method according to the invention and the device according to the invention make it possible to determine the volatile substances simultaneously or at different times in both the liquid and the gaseous phase of such a reaction system, so that, for example, reactant and product concentrations can be advantageously detected in reaction systems in which one or more biochemical reactions
  • the procedure according to the invention and device advantageously allow such a procedure by means of a single device and a method performed therewith.
  • the present invention therefore also provides methods for mass spectrometry
  • Analyzing substances contained in a reaction system constructed from at least one liquid and at least one gaseous phase available, wherein a
  • Method for the mass spectrometric analysis of substances present in liquid and gaseous samples according to the present invention, in particular comprising the steps a) and b), in order to determine the substances, preferably comprising the steps a), a) and a2) and / or in step b) the steps i), ii), iii) and iv).
  • such a reaction system is a bioreactor having at least one liquid reaction medium and at least one gas phase, in particular for the fermentation, the biodegradation of products, the conversion of substances or the production of substances.
  • Concentration of the starting materials and the final products can be determined efficiently by a single device.
  • a liquid and gaseous phase reaction system may be used in the biotechnology, chemical, petrochemical, pharmaceutical, medical, and food industries.
  • the first, the second and the third flow element by a first
  • Valve device preferably directly, interconnected.
  • the third flow element is preferably connected via a second valve device, preferably directly, to the fourth flow element.
  • the first valve device connects in a first Position the first flow element with the third flow element.
  • the first valve device connects the second flow-through element with the third flow-through element.
  • the second valve device preferably connects the third flow-through element to the fourth flow-through element.
  • a second position exists between the third
  • first valve means preferably directly, interconnected.
  • second flow-through element is connected to the third flow-through element by a second valve device, preferably directly.
  • the third flow-through element is connected via a third valve device, preferably directly, to the fourth flow-through element.
  • the first valve device preferably connects the first flow-through element to the third flow-through element.
  • the second valve device preferably connects the second flow-through element to the third flow-through element. In a second position, there is no fluid contact between the second and third flow elements. In a first position, the third valve device preferably connects the third flow-through element to the fourth flow-through element. In a second position, there is no fluid contact between the third and the fourth flow element.
  • first flow-through element with the first third flow-through element is connected to one another by a first valve device, preferably directly.
  • the second is connected to one another by a first valve device, preferably directly.
  • the first valve device preferably connects the first flow-through element to the first third flow-through element in a first position. In a second position, there is no fluid contact between the first flow-through element and the first third flow-through element. In a first position, the second valve device preferably connects the second flow-through element to the second, third flow-through element. In a second position exists between the second fürfiusselement and the second third fürfiusselement no fluid contact.
  • the third valve device In a first position, the third valve device preferably connects the first third flow-through element to the fourth flow-through element. In a second position, the third valve device preferably connects the second third flow-through element to the fourth flow-through element. In a third position, there is no fluid contact between the first third flow-through element, the second third flow-through element and the fourth flow-through element.
  • first flow-through element with the first third flow-through element is connected to one another by a first valve device, preferably directly.
  • the second is connected to one another by a first valve device, preferably directly.
  • the first valve device preferably connects the first flow-through element to the first third flow-through element in a first position. In a second position, there is no fluid contact between the first flow-through element and the first third flow-through element. In a first position, the second valve device preferably connects the second flow-through element to the second, third flow-through element. In a second position, there is no fluid contact between the second flow-through element and the second, third flow-through element. In a first position, the third valve device preferably connects the first third flow-through element to the first, fourth flow-through element. In a second position, there is between the first third fürfiusselement and the first fourth
  • the fourth valve device preferably connects the second third flow-through element to the second, fourth flow-through element. In a second position, there is no fluid contact between the second third flow-through element and the second, fourth flow-through element.
  • each inlet for a gaseous sample or a liquid sample to a third and fourth pass element, wherein only immediately before the mass spectrometer, the different flow element strands are brought together via a valve device.
  • each inlet for a liquid sample has a first flow-through element, third and fourth flow-through elements, and each inlet for a gaseous sample a second one Flow element associated with a third and a fourth flow element, wherein only before the mass spectrometer, the different flow element strands are combined via a valve device.
  • the first, second, third and / or fourth valve device makes it possible in particular for the mass flow of gaseous substances into the third or third and / or fourth (s).
  • the first, second, third and / or fourth valve device preferably has at least one, preferably at least two, preferably exactly one, preferably exactly two valves.
  • the at least one valve is a switching valve, drum valve or a proportional valve.
  • the at least one valve is preferably designed as an electric or pneumatic valve.
  • valves preferably all valves, are controllable, preferably via a software-based control program or a programmable logic controller.
  • a calibration solution is introduced into the first flow element for calibrating the mass spectrometer instead of a liquid sample.
  • a calibration gas or calibration mixture is preferably introduced instead of a gaseous sample, preferably valve-controlled, into the second flow element.
  • the present invention preferably relates to a method wherein the first, the second, the third and / or the fourth flow-through element to a temperature of 60 to 80 ° C, preferably 70 to 75 ° C, heated.
  • the heating of the naturalfiuss institute preferably takes place by a
  • Heating element Preferred is the first, the second, the third and / or the fourth
  • Flow element associated with a respective heating element Preferably, the same temperature is present in the first, the second, the third and / or the fourth flow element.
  • the third flow element or “the fourth flow element” includes one or more flow elements of the same type. Accordingly, these terms also include the first third / fourth and second third / fourth flow elements, if present in the device.
  • heating one or more flow elements is the deposition, preferably condensing, or adsorbing the at least one or more gaseous substances or substances on the inside of the flow element, preferably the conduit, preferably the tube or tube, preferably the metal tube or
  • Metal corrugated tube preferably of stainless steel tube or stainless steel corrugated tube prevented.
  • the present invention preferably relates to a method wherein the optional introduction of the at least one or more substances of the liquid or gaseous sample into the first or second flow element is controlled such that in step al) and / or a2) equal amounts of the at least one or more gaseous substances are present in the third flow element.
  • the term "equal amounts” is understood to mean that, preferably via the control of the valve device, the mass flow from the first flow element into the third flow element and the mass flow from the second flow element into the third flow element by a maximum of ⁇ 10%, preferably maximum differ by ⁇ 5%, preferably at most ⁇ 1%.
  • the term "mass flow” is understood as meaning the mass of the at least one or more substances introduced into the third flow element over a specific time.
  • this special procedure namely by introducing equal amounts of at least one or more gaseous substances in the third flow element, it is particularly possible in a fully automated manner between the first and the second flow element, ie between the introduction of at least one or more substances one
  • At least one or more substances of at least two, preferably at least five, preferably at least ten different liquid samples are preferably introduced via the first flow element via respectively different inlets, preferably with a time offset.
  • At least one, preferably at least two, preferably at least five, preferably at least ten, preferably at most thirty, preferably at most twenty, different substances of a liquid sample are preferably introduced via the first flow element.
  • At least one or more substances of at least two, preferably at least five, preferably at least ten different gaseous samples are preferably introduced via the second flow-through element via respectively different inlets, preferably offset in time.
  • At least one, preferably at least two, preferably at least five, preferably at least ten, preferably at most thirty, preferably at most twenty, different substances of a gaseous sample are preferably introduced via the second flow-through element.
  • the invention preferably relates to a method wherein the pressure in the fourth
  • the pressure in the first, the second, the third and / or the fourth confiusselement is detected.
  • the pressure is detected in both the third and in the fourth confiusselement.
  • This detection is preferably carried out by a respective detection unit.
  • this detection unit is connected to a control unit.
  • the control unit has a software-based
  • the present invention preferably relates to a method, wherein at a detected pressure increase in the fourth Fiusselement one between the third and fourth
  • Controllable valve device is closed so that there is no fluid contact between the third and fourth Naturalfiusselement.
  • a controllable valve device arranged between the third and fourth flow-through element is preferably closed so that there is no fluid contact between the third and the fourth flow-through element.
  • the at least one or more gaseous substances preferably flow out of the fourth flow-through element, preferably directly, into the mass spectrometer, ie into the
  • the present process preferably consists of the abovementioned process steps, preferably of process steps a), al), a2), b), i), ii), iii) and iv).
  • no fractionation of the at least one or more substances present in gaseous form in step a) takes place before they are analyzed by mass spectrometry in step b).
  • the process according to the invention or preferred according to the invention is preferably free of one
  • chromatographic in particular gas chromatographic, fractionation, preferably the at least one or more gaseous substances present.
  • the mass spectrometric analysis of reactions occurring in gases or gas mixtures or liquids preferably takes place.
  • ion currents of the one or more gaseous substances are measured, whereby the respective concentrations of these substances can be calculated.
  • a pump is used in each case, which is in each case designed to generate a corresponding pressure.
  • the liquid sample for introduction into the first flow element on a liquid-impermeable, but gas-permeable, preferably in a membrane device, also referred to as a membrane module present membrane passes such that under the prevailing conditions during the process at least one or several substances volatilized, that is brought into the gas phase, can be. Corresponding substances pass through the membrane and are thereby introduced into the first flow element. It is preferably provided that the liquid in the region of the membrane at a constant temperature, preferably at a temperature between 10 to 30 ° C, preferably 25 ° C is maintained.
  • the temperature for the particular application can be varied.
  • the temperature preferably remains constant during the, preferably entire, measurement period.
  • it is calibrated at the same temperature.
  • the at least one or more substances of the liquid sample are introduced into the first flow element and / or the at least one or more substances of the gaseous sample are introduced into the second flow element such that the first flow element or the second flow element communicates with the third flow element the valve device are fluidically, preferably directly, connected, that is, therefore, due to the present in the third flow element negative pressure a certain
  • the liquid sample guided past the membrane is guided in the branch or secondary branch to the liquid flow to be examined.
  • the liquid sample guided past the membrane is guided in the branch or secondary branch to the liquid flow to be examined.
  • Membrane device for introducing volatile substances from a liquid sample constructed such that it acts as a bypass, wherein the liquid sample is removed from a container or from a conduit by means of a pulsation-poor pump and optionally returned again.
  • the membrane is preferably supported by a porous disc.
  • the membrane is sealed by means of a polytetrafluoroethylene sheathed sealing ring in a membrane housing.
  • the vacuum detection devices which are the third and / or the fourth
  • Vacuum pumps via control circuits, in particular controlled by a control unit connected.
  • Such a determination is carried out by means of a device according to the invention, which has a detector for the determination of non-volatile substances present in a liquid sample.
  • the present invention also relates to a mass spectrometric apparatus
  • Analyzing substances present in liquid and gaseous samples comprising aa) a mass spectrometer,
  • cc at least one inlet for a gaseous sample.
  • the at least one inlet for a liquid sample is different than the at least one inlet for a gaseous sample.
  • the device according to the invention preferably has the above-described
  • Flow elements in particular a the first at least one inlet for a liquid sample downstream flow element and the at least one inlet for a gaseous sample downstream second flow element, and optionally a third and / or fourth flow element, wherein the first flow element is different from the second flow element ,
  • the present invention preferably relates to a device, wherein the device is set up for carrying out a method according to the invention or preferred according to the invention.
  • the process according to the invention or preferred according to the invention is preferably carried out using a device according to the invention or preferred according to the invention.
  • the present device according to the invention is characterized in that it is a very compact and dead volume device.
  • the present invention preferably relates to a device, wherein the at least one inlet for a liquid sample has a hydrophobic, at least partially porous membrane. This membrane is preferably located in a membrane device.
  • the membrane is preferably a hydrophobic membrane.
  • the membrane preferably has a plurality of pores, wherein the average pore radius preferably has a value of 0.001 to 0.1 ⁇ , preferably 0.01 to 0.05 ⁇ .
  • the membrane preferably has a thickness of 1 to 100 ⁇ , preferably 10 to 80 ⁇ , preferably 40 to 60 ⁇ on.
  • the membrane preferably has a porosity of 40 to 80%, preferably 50 to 70%.
  • the membrane is preferably a pervaporation membrane, preferably a polytetrafluoroethylene (PTFE) membrane or a silicone membrane, preferably a polydimethylsiloxane (PDMS) membrane, preferably a polytetrafluoroethylene (PTFE) membrane.
  • PTFE polytetrafluoroethylene
  • PDMS polydimethylsiloxane
  • Dense pervaporation membranes preferably a silicone membrane, preferably a PDMS membrane, are also preferably used as the membrane.
  • a PTFE membrane is used as the inlet for at least one volatilizable substance from a liquid sample in a fermentation process or cell culture process, in particular as an integral part of a fermentation process or cell culture process container, preferably a corresponding disposable container.
  • the invention preferably relates to a device which additionally has at least one inlet for a calibration medium.
  • the present invention preferably relates to a device comprising at least one valve device which is arranged between the inlets and the mass spectrometer.
  • the at least one valve device is arranged spatially and / or functionally between the inlets and the mass spectrometer.
  • the present invention preferably relates to a device, wherein the at least one inlet for a liquid sample is designed as an in situ sensor.
  • the present device has a membrane device designed as an in situ sensor.
  • This in situ sensor serves, in particular, to extract the volatilizable substances from this medium directly in a liquid reaction medium or in a liquid medium, so that these substances can be introduced into the first flow element.
  • this in situ sensor can be used in biotechnology, in particular in the form of an Ingold nozzle. He is considered
  • the in-situ sensor has a cylindrical inner part with external thread and a sleeve with internal thread, it preferably consists thereof, wherein the cylindrical inner part is screwed into the sleeve, wherein the internal thread and the external thread cooperate.
  • the inner member also has a longitudinally extending conduit, preferably bore, whereby there is fluid communication between the liquid medium or sample and the inlet of the liquid sample device.
  • this line is electropolished.
  • adsorption that is to say the condensation of the gaseous substances present through the membrane on the surface of this line, is advantageously avoided.
  • the in situ sensor preferably has a heating element, so that the entire sensor can be heated and is also heated during use in the method preferred according to the invention or in accordance with the invention.
  • the membrane is clamped by means of a suitable seal, preferably O-ring seal, between the inner part and the sleeve, preferably by screwing the sleeve.
  • the sleeve has at this end an opening, preferably bore, so that the liquid sample in sufficient quantity
  • the membrane can wet. Accordingly, the only intended path of the liquid, ie the liquid sample, is into the first flow element intended solely by way of the membrane.
  • This membrane is preferably used in the in situ sensor, that a, preferably slight, outward curvature, ie in
  • a wiper element is preferably provided alternatively or additionally.
  • this membrane is supported by a disk, preferably a sintered disk, preferably against the curvature.
  • Reactor interior preferably fermenter interior flush, preferably liquid-tight, preferably fluid-tight, from.
  • the liquid flow and the pressure at the membrane are preferred in the process according to the invention or preferred according to the invention
  • the in situ sensor can also be designed as a flow sensor, which is preferably installed in a pipe, preferably in a pipe.
  • the in situ sensor can also be integrated in a stirrer, a baffle or in the reactor wall of a reaction vessel.
  • the in situ sensor is preferably used as an integral part of a fermentation process or cell culture process container, preferably a corresponding disposable container.
  • the intended for receiving the membrane in situ sensor is preferably made of plastic, preferably PTFE, or other materials.
  • the membrane may be constructed of the same or different material.
  • the present invention preferably relates to a device, wherein the at least one inlet for a gaseous sample is designed as a capillary inlet.
  • the present invention preferably relates to a device, wherein the capillary inlet has a quartz-coated and heatable capillary.
  • the present invention preferably relates to a device, wherein the mass spectrometer comprises an ion source, an analyzer and a detector.
  • the present invention preferably relates to an apparatus wherein the mass spectrometer is a quadrupole mass spectrometer.
  • the present invention preferably relates to a device, wherein the mass spectrometer is a process mass spectrometer.
  • the device comprises a membrane device for volatilizing substances present in a liquid sample, a capillary for the admission of a gaseous sample and an in situ sensor for the inlet of a liquid sample, preferably these components are cross-linked and switchable Valves connected and automatically controlled.
  • the device comprises at least two membrane devices for volatilizing substances present in a liquid sample and a capillary for the inlet of a gaseous sample, wherein at least one membrane device is designed as an in situ sensor for the inlet of a liquid sample.
  • the device is constructed as a transportable and self-sufficient module.
  • the present device is preferably present in a transportable housing.
  • the device can be integrated into existing processes.
  • the present device is in particular able to supply different samples, both gaseous and liquid samples and calibration media, preferably calibration solutions, to a mass spectrometric analysis or determination of substances present in gaseous form without conversion of the device.
  • the device also has an inlet for an acid or a base.
  • an acid or base increases the sensitivity of the mass spectrometer to certain substances by improving their volatility by protonation or deprotonation, depending on the pKa value of the substance to be measured.
  • the acid or base is first introduced by means of a pump into the liquid sample, in particular when the membrane device is mounted in a bypass.
  • the use of two low-pulsation pumps allows the introduction of an acid or base in the bypass.
  • a mass spectrometric analysis or determination of correspondingly volatile substances can be carried out alternately both from a liquid sample and from a gaseous sample without conversion measures.
  • One or more further inlets for gaseous and / or liquid samples may be provided by means of at least one releasable flow element connection, also called a flange, which has a valve device.
  • the present device preferably has at least one heating element per flow element present.
  • these heating elements in particular a uniform temperature profile can be ensured in order to prevent the adsorption or condensation of the gaseous substances on the inside of the through-flow elements, in particular of the line.
  • all fürfiussetti and valve devices in particular all surfaces with which the gaseous substances can come into contact, electropolished.
  • electropolishing By electropolishing the adsorption or condensation of the gaseous substances is also avoided.
  • the device according to the invention or preferred according to the invention has in particular a control system. Through the control system is communication with the
  • Mass spectrometric analysis of the substances to be analyzed are supplied.
  • Process parameters are preferably transmitted to the control system.
  • a pressure drop or pressure increase can be detected and thus registered and thus suspected on an accident, for example, liquid burglary, a part or all valves in the
  • Mathematical models are preferably stored in the control system, whereby ion currents are converted into concentrations on the basis of an automatic calibration. On the user interface of the control system, the required parameters for the
  • the control system preferably has an automated
  • Calibration program With the control system certain procedures can be programmed. In particular, the intervals between the measurement of a gaseous sample, a liquid sample or a calibration medium can be determined, in particular via the control of the various valves.
  • At least one interface is also integrated in the device, whereby the presently measured mass spectrometric values can be transmitted to higher-level control systems, in particular reactor control systems. It is likewise possible to transmit measured values, in particular the pH, oxygen and carbon dioxide partial pressures, conductivity, amount of added substances and optical density measured in a reaction medium, by appropriate interfaces of other measuring devices.
  • the device according to the invention therefore comprises, in particular, a control system which has interfaces for further devices, for example for the reception of
  • the control system used according to the invention has a compact design.
  • the control system preferably has interfaces for input and output of
  • Interfaces to process control systems interfaces to a calibration module or has an integrated calibration, in particular for automatic Calibration of the components to be measured under control of valves, pumps and sensors, in particular with regard to valve positions for the status of the calibration solution and the temperature and at least one communication device to the mass spectrometer itself, the pumps used in particular high vacuum and roughing pumps and, preferably via the valves to which at least one inlet for a liquid sample and the at least one inlet for a gaseous sample and optionally to further inlets for further gas or liquid samples.
  • the pumps used in particular high vacuum and roughing pumps and, preferably via the valves to which at least one inlet for a liquid sample and the at least one inlet for a gaseous sample and optionally to further inlets for further gas or liquid samples.
  • a display in particular a touch screen.
  • further measured variables preferably the living cell count of microorganisms, are preferably estimated via a soft sensor.
  • soft sensor (composed of the words “software” and “sensor”), also referred to as a virtual sensor or sensor fusion, does not mean a sensor that actually exists, but a dependency simulation of representative measured variables to a target size measured directly on the basis of their correlating parameters and a model of the correlation
  • a virtual sensor or sensor fusion does not mean a sensor that actually exists, but a dependency simulation of representative measured variables to a target size measured directly on the basis of their correlating parameters and a model of the correlation
  • the device according to the invention for the mass spectrometric analysis of substances present in liquid and gaseous samples comprises aa) a mass spectrometer, bb) at least one inlet for a liquid sample, cc) at least one inlet for a gaseous sample and additionally a detector for the, in particular quantitative and / or qualitative, determination of nonvolatile substances present in a liquid sample.
  • the device according to the invention is thus preferably capable of mass spectrometry on the one hand the volatile substances in the liquid and / or gaseous phase of a
  • the detector is an optical detector, an electromagnetic radiation detector or an ultrasonic detector.
  • reactions can be analyzed and recorded in real time with the present device.
  • in real time means that within seconds, preferably within one second, the at least one introduced substance can be analyzed.
  • the product concentration in fermentations can be determined in real time by measuring the resulting products without much effort and accurately. Accordingly, with the real-time measurement of the products and by-products, the fermentation
  • the measurement of the partial pressures of C0 2 and 0 2 is frequently measured in order to infer cell growth and product formation rate.
  • the total composition of the exhaust gas including the products can be measured.
  • the gas-dissolved concentration of C0 2 and oxygen and all other volatile substances from the fermentation broth can be measured through the inlet for the liquid sample.
  • the device is suitable for measuring a wide variety of products, and can therefore also be used for different production processes, which correspond to one
  • the present device can be implemented as a tailored analyzer integrated with production equipment.
  • ethanol is contaminated by methanol, acetaldehyde, ethyl acetate and diacetyl. With the present device, these can
  • Contaminants are detected. It can therefore be used as an analyzer for the detection of volatile contamination, that is, for quality control.
  • the device according to the invention can therefore preferably be used in beer production.
  • the present device may be used in research and development,
  • Process monitoring of all types of process media with volatile components to quality control for example in the branches of the chemical industry, petrochemical, biotechnology, pharmacy, medical technology and food industry. It can be used in laboratory and / or pilot plants, production plants, in particular for the optimization of the production process taking place there. It can also be used in productions in modular and flexible systems
  • this device is also suitable for quality assurance in sensitive production areas and for monitoring drinking water and / or wastewater.
  • the device has low response times and the ability to measure up to 30, preferably 20 substances at the same time on.
  • the present device can be used in industrial biotechnology and in bio-based production as a measuring device for process analysis.
  • the device can be used in enzymatic processes, for example in the production of butanediol, Propandiol, succinic acid, ethanol from lignocellulose, butanol, polyols, butyl acrylate, thiols, esters, lactic acid are used.
  • the device can be used in medical technology, for example, to be able to measure the gas composition of the respiratory air, the gas emission of the skin and all volatile components directly from the blood.
  • Mass spectrometric analysis also referred to as an analysis device for short, is understood to be complementary to one another. Method steps of the analysis method which have been described explicitly or implicitly in connection with the analysis apparatus are preferably individually or combined with one another. Steps of a preferred embodiment of the invention
  • Analyzer This is preferably characterized by at least one feature which is characterized by at least one step of a preferred embodiment of the
  • Analytical method is conditional.
  • the analysis method is preferably characterized by at least one method step, which is caused by at least one feature of the analysis apparatus.
  • Figure 1 is a schematic representation of a preferred device according to the invention for mass spectrometric analysis of both liquid and gaseous samples
  • Figure 2 is designed as Ingold nozzle in situ sensor according to the present invention
  • FIG. 3 shows ion flows (IC) in [A] of various substances over the time t in [min] during the incineration of a carbon fiber
  • FIG. 4 shows ion currents (IC) in [A] of various gases present in a so-called reed switch over the time t in [s]
  • FIG. 5 shows a measured enzyme kinetics and a mathematical modeling based on a hyperbolic velocity equation
  • Figure 6 is a schematic representation of a preferred alternative according to the invention.
  • FIG. 1 shows a device 1 in which a liquid sample from a sampling chamber and inlets 4, 6 having lines 5 and 7 can be introduced in each case into a gaseous sample via an inlet 2 having a line 3.
  • a calibration solution stored in a container 9 can be introduced via an inlet 8 having a line 11.
  • Calibration solution is fed by means of a pump P401 a membrane device M401.
  • the pump P401 is characterized by a flow rate of 0 to 50 milliliters per minute, preferably 10 milliliters per minute, and can thus produce a system pressure of 0 to 400 bar.
  • Via a, preferably pneumatic, valve V401 can optionally the liquid sample on the
  • Line 3 or the calibration solution via the line 11 by means of the pump P401 be supplied in liquid form to the membrane device M401.
  • the liquid sample or the calibration solution flows parallel to a membrane 13 present in the membrane device M401.
  • the membrane 13 is preferably a hydrophobic, at least partially porous membrane, by means of which volatile substances which are present in the calibration solution or the liquid sample can be converted into a gaseous state of aggregation.
  • the non volatilizing or moistening of the membrane 13 serving liquid content is discharged via a line 15 either into a container 17 or via a line 16 into the sampling chamber
  • the volatilized substances of the liquid sample or of the calibration solution are present in gaseous form in a first flow element 19, preferably a line 19.
  • the first flow element 19 preferably a line 19.
  • the Jerusalem Indian Fiusselement 19 is preferably heated by a heating element H401.
  • the lines 5 and 7 provided for the gaseous samples can likewise be heated via heating elements H301 and H302.
  • the gaseous samples may optionally be over pneumatic, valve V301 or a, preferably pneumatic, valve V302 in a second Naturalfiusselement 21, preferably a conduit 21, are introduced.
  • Substances are introduced into a third fürfiusselement 23.
  • the introduction takes place on the one hand by appropriate switching and opening of the valves V201 and V202 and on the other hand additionally by the suction generated by a pump P101.
  • a pre-vacuum that is to say a pressure of 0.01 to 0.5 mbar, is produced by the pump P101.
  • Via a manual valve VH101 enter the gaseous substances from the third fürfiusselement 23 in a fourth fürfiusselement 25.
  • the manual valve VH101 can also be designed as a valve operable via a control.
  • the fourth confiusselement 25 is associated with 02, which is particularly suitable for producing a high vacuum, that is for generating a vacuum with a pressure of 10 "5 mbar or less a pump PI.
  • this a PIRSA- pressure gauge PIRSA102 assigned.
  • PIRSA101 and PIRSA102 PIRSA pressure gauges are used to measure, record and, if necessary, alarm the pressure present in the third and fourth flow elements 23 and 25 if the actual pressure differs from a preset setpoint pressure
  • All the heating elements H101, H201, H301, H302, H401 serve, in particular, to prevent fogging, that is to say condensation or adsorption of the substances present in gaseous form at the corresponding flow-through elements in a mass spec trometer 29 present filament F101, whereby the gaseous substances are ionized.
  • the generated ions are accelerated by a static, electric field and fly centrally through four parallel rod electrons whose intersections with a plane perpendicular to the cylinder axis form a square, the so-called quadrupole 27.
  • a m / e- Selection takes place, so that only particles with a defined mass can pass through the field.
  • the ions in a detector El 01 with measuring amplifier, which measures the ion current and is converted by the software of the connected PC to count rate or partial pressure.
  • the detector El 01 is a photomultiplier E101 1 (abbreviated as SEM or SEV). He also has a Faraday catcher
  • the pressure gauge PIRSA101 and the pumps P101 and P102 are each connected to drive electronics via an RS485 interface.
  • the elements of the device marked with the symbol A can be controlled by a digital or analog programmable logic controller.
  • the elements marked with a symbol B have an OPC connection.
  • the elements marked with a symbol C have an RS485 interface connection and the elements marked with the symbol D have an external connection but no connection to the stored-program controller.
  • Figure 2 shows an in situ sensor 100 having a cylindrical inner part 101 with invisible external thread and a sleeve 102 with invisible internal thread, wherein the cylindrical inner part 101 is screwed into the sleeve 102, wherein the internal thread and the external thread cooperate.
  • the inner member 101 also has a longitudinally extending invisible line, preferably a bore, whereby there is fluid communication between the liquid medium or sample and the inlet of the liquid sample device.
  • the in situ sensor 100 has a heating element, so that the entire sensor 100 can be heated.
  • a membrane 109 is clamped by means of a suitable seal, preferably O-ring seal, between the inner part 101 and the sleeve 102, preferably by
  • the sleeve 102 has an opening, preferably bore, at this end of the membrane, so that the liquid sample can wet the membrane in a sufficient amount when used as intended.
  • This membrane 109 is preferably used in the in situ sensor 100 in such a way that a, preferably slight, curvature results to the outside, that is to say in the direction of the liquid or sample. This preferred curvature improves the
  • a wiper element is preferably provided alternatively or additionally.
  • this membrane 109 is supported by a non-visible disc, preferably a sintered disc, preferably against the curvature.
  • the in situ sensor is preferably attached to a reaction vessel, preferably attached to a fermenter and preferably includes a on the sleeve 102 externally applied ring seal 111 with the reactor interior, preferably
  • FIG. 3 shows ion currents (IC) in [A] over the time t in [min] during the incineration of a
  • the curve 200 shows the ionic current of C0 2
  • the curve 201 shows the ionic current of hydrogen
  • the curve 202 of benzene shows the ionic current of hydrogen
  • the curve 202 of benzene shows the ionic current of hydrogen
  • the curve 202 of benzene shows the ionic current of hydrogen
  • the curve 202 of benzene shows the ionic current of hydrogen
  • the curve 203 of aliphatic hydrocarbons the curve 204 of aromatic hydrocarbons.
  • FIG. 4 shows the ion currents (IC in [A]) over the time t in [s] of various in a reed
  • FIG. 5 shows the methanol concentration in the enzymatic production of methanol and formic acid from formaldehyde.
  • Mass spectrometer is the conversion of the ion currents to concentrations possible. Due to the high data density of the kinetics, a mathematical modeling of the enzyme reaction is possible. Accordingly, FIG. 5 shows the methanol concentration c in g / 1 over the
  • FIG. 6 shows an alternative device 1, which corresponds to the device shown in FIG. 1, but with an in situ sensor 100, introduced into a non-illustrated sensor 100
  • the inlet for a liquid sample into the first flow element 19 represents.
  • the volatile substances to be analyzed are transferred from the liquid sample to the gaseous state and introduced into the first flow element 19.

Abstract

L'invention concerne un procédé pour effectuer avec un spectromètre de masse une analyse d'échantillons liquides et/ou gazeux ainsi qu'un dispositif (1) pour la mise en œuvre de ce procédé. Selon l'invention, on emploie un spectromètre de masse (29) qui comprend un premier élément de passage (19) pour des échantillons liquides et un deuxième élément de passage (21) pour des échantillons gazeux.
PCT/EP2016/060055 2015-05-05 2016-05-04 Spectromètre de masse en ligne pour la détection en temps réel de composants volatiles provenant de la phase gazeuse et liquide aux fins d'analyse de processus WO2016177810A1 (fr)

Priority Applications (2)

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US15/568,627 US10361072B2 (en) 2015-05-05 2016-05-04 Online mass spectrometer for real-time detection of volatile components from the gas and liquid phase for process analysis
EP16721783.5A EP3292563B1 (fr) 2015-05-05 2016-05-04 Spectromètre de masse en ligne pour la détection en temps réel de composants volatiles provenant de la phase gazeuse et liquide aux fins d'analyse de processus

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DE102015208250.4 2015-05-05
DE102015208250.4A DE102015208250A1 (de) 2015-05-05 2015-05-05 On-line Massenspektrometer zur Echtzeiterfassung flüchtiger Komponenten aus der Gas- und Flüssigphase zur Prozessanalyse

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US11581177B2 (en) * 2018-07-25 2023-02-14 Perkinelmer Health Sciences Canada, Inc. System for introducing particle-containing samples to an analytical instrument and methods of use
CN114113428A (zh) * 2021-11-12 2022-03-01 云南电网有限责任公司电力科学研究院 一种测试液体有机储氢材料的装置及方法

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EP3292563A1 (fr) 2018-03-14
US10361072B2 (en) 2019-07-23
EP3292563B1 (fr) 2023-11-08
EP3292563C0 (fr) 2023-11-08
DE102015208250A1 (de) 2016-11-10

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